CN114450335A - Rubber composition, rubber-metal composite, tire, conveyor belt, hose, and crawler belt - Google Patents
Rubber composition, rubber-metal composite, tire, conveyor belt, hose, and crawler belt Download PDFInfo
- Publication number
- CN114450335A CN114450335A CN202080067811.7A CN202080067811A CN114450335A CN 114450335 A CN114450335 A CN 114450335A CN 202080067811 A CN202080067811 A CN 202080067811A CN 114450335 A CN114450335 A CN 114450335A
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- Prior art keywords
- rubber
- metal
- acid
- rubber composition
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 149
- 239000005060 rubber Substances 0.000 title claims abstract description 149
- 239000000203 mixture Substances 0.000 title claims abstract description 95
- 239000002905 metal composite material Substances 0.000 title claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 141
- 239000002184 metal Substances 0.000 claims abstract description 141
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 52
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000004636 vulcanized rubber Substances 0.000 claims abstract description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 27
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 27
- 239000004332 silver Substances 0.000 claims abstract description 27
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 25
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 25
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 25
- 239000010955 niobium Substances 0.000 claims abstract description 25
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 25
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 23
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 aliphatic monocarboxylic acid Chemical class 0.000 claims description 50
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 14
- 229920001194 natural rubber Polymers 0.000 claims description 14
- 244000043261 Hevea brasiliensis Species 0.000 claims description 13
- 229920003052 natural elastomer Polymers 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 11
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 7
- 235000021314 Palmitic acid Nutrition 0.000 claims description 7
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 7
- MIIBUHIQXLFJFP-UHFFFAOYSA-N 3-methyl-1-[[3-[(3-methyl-2,5-dioxopyrrol-1-yl)methyl]phenyl]methyl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1CC1=CC=CC(CN2C(C(C)=CC2=O)=O)=C1 MIIBUHIQXLFJFP-UHFFFAOYSA-N 0.000 claims description 6
- HPTJCEPNQHYWIH-UHFFFAOYSA-N 3-hydroxy-n-(4-methylpentan-2-ylideneamino)naphthalene-2-carboxamide Chemical compound C1=CC=C2C=C(O)C(C(=O)NN=C(C)CC(C)C)=CC2=C1 HPTJCEPNQHYWIH-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- DGPKJHGPIAETKL-UHFFFAOYSA-N 2,2-bis(sulfanylidene)-1,3,2-dioxathionane;sodium;dihydrate Chemical compound O.O.[Na].[Na].S=S1(=S)OCCCCCCO1 DGPKJHGPIAETKL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 10
- 229910000831 Steel Inorganic materials 0.000 description 31
- 239000010959 steel Substances 0.000 description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 24
- 229910017052 cobalt Inorganic materials 0.000 description 23
- 239000010941 cobalt Substances 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 239000002131 composite material Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 238000007747 plating Methods 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 229920003244 diene elastomer Polymers 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 229920001195 polyisoprene Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 150000004683 dihydrates Chemical class 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000006237 Intermediate SAF Substances 0.000 description 2
- 229920001967 Metal rubber Polymers 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- DBQFKMXHMSMNRU-UHFFFAOYSA-N [Zn].[Co].[Cu] Chemical compound [Zn].[Co].[Cu] DBQFKMXHMSMNRU-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N bismuth(III) nitrate Inorganic materials [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
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- 238000004898 kneading Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
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- 239000003921 oil Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
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- 229920005989 resin Polymers 0.000 description 2
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- DTOSIQBPPRVQHS-UHFFFAOYSA-N α-Linolenic acid Chemical compound CCC=CCC=CCC=CCCCCCCCC(O)=O DTOSIQBPPRVQHS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D55/00—Endless track vehicles
- B62D55/08—Endless track units; Parts thereof
- B62D55/18—Tracks
- B62D55/24—Tracks of continuously flexible type, e.g. rubber belts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
- B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
- B65G15/30—Belts or like endless load-carriers
- B65G15/32—Belts or like endless load-carriers made of rubber or plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Transportation (AREA)
- General Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The method comprises the following steps: a rubber composition capable of giving a vulcanized rubber having a high modulus and excellent rubber-metal adhesion; a rubber-metal composite excellent in durability and rubber-metal adhesion; and a tire, a conveyor belt, a hose, and a crawler belt excellent in durability. The rubber composition comprises: a rubber component; a rubber-to-metal adhesion promoter comprising at least one selected from the group consisting of: a metal carboxylate (1) having 2 to 25 carbon atoms and including a metal species selected from the group consisting of bismuth, copper, antimony, silver, niobium and zirconium; and a compound (2) represented by the formula (A); and 4,4' -diphenylmethane bismaleimide.
Description
Technical Field
The present invention relates to a rubber composition, a rubber-metal composite, a tire, a conveyor belt, a hose, and a crawler.
Background
Due to recent environmental regulations, research into alternatives to cobalt salts (e.g., cobalt stearate, cobalt versatate) that are commonly used as rubber-metal adhesion promoters is urgently needed.
For example, disclosed is a rubber-metal adhesion promoter comprising (1) a metal salt of an aliphatic carboxylic acid having 2 to 25 carbon atoms, wherein the metal is bismuth, copper, antimony, silver or niobium, or (2) a compound represented by the following general formula (a), wherein Z is a structure selected from the following formulae (Z-1) to (Z-4), M is bismuth, copper, antimony, silver or niobium, (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, and x is (valence-1 of M) (for example, see PTL 1).
An average formula is disclosed: an organometallic compound of X (OMA 'p) M (OMB' p) N, wherein M is cobalt, nickel or bismuth, B 'is a residue of an aromatic carboxylic acid having 7 to 11 carbon atoms, A' is a residue of an aliphatic carboxylic acid having 7 to 11 carbon atoms, p is 1 when M is cobalt or nickel, or p is 2, N is 0.5 to 2 when M is bismuth, and M is (3-N) (for example, see PTL 2).
Disclosed is a method for increasing the viscosity of or gelling an aqueous medium containing a gellable polymeric substance having a phenolic hydroxyl substituent, wherein an effective amount of laccase is added to the aqueous medium (for example, see PTL 3).
Also disclosed is a steel cord/rubber composite (see PTL 4, for example), in which rubber and a steel cord having one or more steel wires coated with plated layers containing copper, zinc, and cobalt are bonded to each other, and when a layer of the plated layers in which a compound of copper and sulfur is present is defined as a bonding layer, the sum (nm) of cobalt-rich regions of six points is greater than 40% of the sum of analyzed areas of the six points, the sulfur content in the bonding layer is analyzed in a perpendicular direction with respect to a steel wire longitudinal direction from the plated layers to the rubber, the position of an inflection point at which the sulfur content increases is defined as the lowermost portion of the bonding layer, the cobalt content in atomic percent is analyzed at six points disposed at equal intervals in the steel wire longitudinal direction from the lowermost portion of the bonding layer to a distance of 100nm inward perpendicular to the steel wire longitudinal direction, and a region having a cobalt content in atomic percent higher than that of the entire plating layer is regarded as a cobalt-rich region (nm).
Reference list
Patent document
PTL 1：WO2016/039375
PTL 2：JP 1992-230397 A
PTL 3：JP 1998-502962 T
PTL 4：WO2016/203886
Disclosure of Invention
Problems to be solved by the invention
The bismuth salts and the like described in PTLs 1 to 4 can obtain rubber-metal adhesion, but reduce the modulus of elasticity of vulcanized rubber, and therefore, many problems of satisfying both the rubber-metal adhesion and the durability of vulcanized rubber are to be solved.
In view of the above circumstances, an object of the present invention is to provide a rubber composition that gives a vulcanized rubber having a high modulus and excellent rubber-metal adhesion, to provide a rubber-metal composite excellent in durability and rubber-metal adhesion, and to provide a tire, a conveyor belt, a hose, and a crawler belt excellent in durability, and to solve the above problems to achieve the object.
Means for solving the problems
<1> a rubber composition comprising: a rubber component, 4' -diphenylmethane bismaleimide, and a rubber-to-metal adhesion promoter comprising at least one selected from the group consisting of: (1) a metal carboxylate having 2 to 25 carbon atoms, and wherein the metal species is selected from the group consisting of bismuth, copper, antimony, silver, niobium, and zirconium; and (2) a compound represented by the following formula (a):
in the formula (A), Z is a structure selected from the group consisting of formulae (Z-1) to (Z-4), M is bismuth, copper, antimony, silver, niobium or zirconium, (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, and x is an integer of (valence-1 of M).
<2> the rubber composition according to <1>, which further comprises at least one selected from the group consisting of disodium hexamethylenedithiosulfate dihydrate, 1, 3-bis (citraconimidomethyl) benzene, 3-hydroxy-N' - (1, 3-dimethylbutylidene) -2-naphthoic acid hydrazide.
<3> the rubber composition according to <1> or <2>, which comprises a filler comprising at least one selected from the group consisting of carbon black and silica.
<4> the rubber composition according to any one of <1> to <3>, wherein the rubber component comprises a natural rubber.
<5> the rubber composition according to any one of <1> to <4>, wherein the rubber-metal adhesion promoter contains the metal carboxylate (1), and the metal species of the metal carboxylate (1) is bismuth or copper.
<6> the rubber composition according to any one of <1> to <5>, wherein the rubber-metal adhesion promoter contains the metal carboxylate (1), and the aliphatic carboxylic acid in the metal carboxylate (1) is an aliphatic monocarboxylic acid or an aliphatic dicarboxylic acid.
<7> the rubber composition <6>, wherein the aliphatic monocarboxylic acid is a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms.
<8> the rubber composition according to <7>, wherein the saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms is 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid.
<9> the rubber composition according to any one of <1> to <8>, wherein the rubber-metal adhesion promoter comprises the compound (2), and M in the compound (2) is bismuth or copper.
<10> the rubber composition according to any one of <1> to <9>, wherein the rubber-metal adhesion promoter comprises the compound (2), and Z in the compound (2) is a structure represented by formula (Z-1).
<11> the rubber composition according to any one of <1> to <10>, wherein the rubber-metal adhesion promoter comprises the compound (2), and (RCOO) in the compound (2) is a residue of a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms.
<12> the rubber composition according to <11>, wherein (RCOO) in the compound (2) is a residue of 2-ethylhexanoic acid, a residue of neodecanoic acid, a residue of hexadecanoic acid or a residue of octadecanoic acid.
<13> a rubber-metal composite comprising the vulcanized rubber of the rubber composition according to any one of <1> to <12> and a metal.
<14> a tire comprising the rubber-metal composite of <13 >.
<15> a conveyor belt comprising the rubber-metal composite body <13 >.
<16> a hose comprising the rubber-metal composite of <13 >.
<17> a crawler belt comprising the rubber-metal composite body <13 >.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a rubber composition which gives a vulcanized rubber having a high modulus and excellent rubber-metal adhesion, and a rubber-metal composite excellent in durability and rubber-metal adhesion, and a tire, a conveyor belt, a hose, and a crawler excellent in durability.
Detailed Description
Hereinafter, the present invention will be described in detail based on embodiments thereof. In the following description, a numerical range represented by "a to B" means a range including a numerical value a and a numerical value B as minimum and maximum values, and represents "a or more and B or less (in the case of a < B), or" a or less and B or more (in the case of a > B).
Parts by mass and% by mass are the same as parts by weight and% by weight, respectively.
< rubber composition >
The rubber composition of the present invention comprises a rubber component, 4' -diphenylmethane bismaleimide, and a rubber-metal adhesion promoter, which comprises at least one selected from the group consisting of: (1) a metal carboxylate having 2 to 25 carbon atoms, and wherein the metal species is selected from the group consisting of bismuth, copper, antimony, silver, niobium, and zirconium; and (2) a compound represented by the following formula (a):
in the formula (A), Z is a structure selected from the group consisting of formulae (Z-1) to (Z-4), M is bismuth, copper, antimony, silver, niobium or zirconium, (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, and x is an integer of (valence-1 of M).
When a compound containing a metal such as bismuth is used as a substitute for a cobalt-containing compound for the adhesive for rubber-metal adhesion, the modulus of elasticity of the vulcanized rubber is lowered although the rubber-metal adhesion can be obtained. In contrast, the rubber composition of the present invention having the above-described constitution can provide a rubber composition which gives a vulcanized rubber having a high modulus and excellent rubber-metal adhesion, and a rubber-metal composite excellent in durability and rubber-metal adhesion, and a tire excellent in durability. The reason for this is not clear, but it is considered that the use of the rubber-metal adhesion promoter containing bismuth or the like and 4,4' -diphenylmethane bismaleimide as described above can supplement and thereby increase the elastic modulus of the vulcanized rubber, and therefore, the rubber-metal adhesion of the vulcanized rubber can be excellent and the durability of the rubber-metal composite can be excellent.
In particular, even when an unvulcanized rubber-metal composite (referred to as a rubber-metal composite precursor) is formed by using the rubber composition of the present invention and the composite is vulcanized to a rubber-metal composite after a lapse of time, the resulting rubber-metal composite can be prevented from metal corrosion and is excellent in rubber-metal adhesion and durability.
The treatment of contacting the rubber compositions with metal and subsequently leaving them to stand for a predetermined time (e.g., 1 week) may be referred to as "uncured aging".
The rubber composition of the present invention can prevent corrosion of uncured aged metal as compared with a rubber composition containing a cobalt-containing material. Therefore, for example, in the case where the metal cord is covered with the rubber composition and the rubber composition is vulcanized after a certain time has elapsed to manufacture the rubber-metal composite, the decrease in the rubber-metal adhesion caused by metal corrosion can be prevented, and the durability of the rubber-metal composite can also be prevented.
Hereinafter, the rubber composition, the rubber-metal composite and the tire of the present invention are described in detail.
[ rubber component ]
The rubber composition of the present invention contains a rubber component.
The rubber component includes at least one diene rubber selected from Natural Rubber (NR) and synthetic diene rubbers. The rubber component may be modified.
Specifically, the synthetic diene rubber includes polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), butadiene-isoprene copolymer rubber (BIR), styrene-isoprene copolymer rubber (SIR), styrene-butadiene-isoprene copolymer rubber (SBIR), and modified rubbers thereof.
From the viewpoint of adhesiveness between the metal and the vulcanized rubber, the diene-based rubber is preferably natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, and isobutylene-isoprene rubber, and modified rubbers thereof, more preferably natural rubber, polyisoprene rubber and polybutadiene rubber, and even more preferably natural rubber and polyisoprene rubber.
The diene rubber may be used alone or in combination of two or more.
From the viewpoint of improving the adhesion between the metal and the vulcanized rubber and improving the durability of the resulting rubber-metal composite, it is preferable that the rubber component contains the natural rubber in an amount of 55 mass% or more, more preferably 65 mass% or more, and even more preferably 75 mass% or more. The upper limit of the natural rubber in the rubber component may be 100 mass%.
From the viewpoint of improving the adhesion between the metal and the vulcanized rubber and improving the durability of the resulting rubber-metal composite, the rubber component preferably uses Natural Rubber (NR) and polyisoprene rubber (IR) in combination, and the ratio of the two (mass of natural rubber/mass of polyisoprene rubber) is preferably from 55/45 to 95/5, more preferably from 65/35 to 93/17, even more preferably from 70/30 to 90/10.
The rubber component may contain a non-diene rubber within a range not to impair the advantageous effects of the present invention.
[ rubber-Metal adhesion promoter ]
The rubber composition of the present invention comprises a rubber-metal adhesion promoter comprising at least one selected from the group consisting of: (1) a metal carboxylate having 2 to 25 carbon atoms, and wherein the metal species is selected from the group consisting of bismuth, copper, antimony, silver, niobium, and zirconium; and (2) a compound represented by the following formula (a):
in the formula (A), Z is a structure selected from the group consisting of formulae (Z-1) to (Z-4), M is bismuth, copper, antimony, silver, niobium or zirconium, (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, and x is an integer of (valence-1 of M).
The metal carboxylate (1) is a metal salt of an aliphatic carboxylic acid having 2 to 25 carbon atoms. Here, the metal species is bismuth, copper, antimony, silver, niobium or zirconium. Among the metal species, bismuth, copper, antimony, or silver is preferable, and bismuth and copper are more preferable, from the viewpoint that an adhesion promoter capable of providing good adhesion between the steel cord and the rubber can be provided even under wet heat conditions.
When the number of carbon atoms of the metal carboxylate (1) is less than 2, the compatibility between the metal carboxylate (1) and the rubber component is poor, and therefore, high adhesion between the vulcanized rubber and the metal cannot be obtained. When the number of carbon atoms is more than 25, the metal carboxylate (1) is difficult to synthesize.
Examples of the aliphatic carboxylic acid having 2 to 25 carbon atoms include aliphatic monocarboxylic acids and aliphatic dicarboxylic acids. The number of carbon atoms of the aliphatic carboxylic acid is the number including the number of carbon atoms of the carboxyl group.
Examples of the aliphatic carboxylic acid having 2 to 25 carbon atoms include saturated aliphatic monocarboxylic acids and unsaturated aliphatic monocarboxylic acids.
Examples of saturated aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, enanthic acid, caprylic acid, pelargonic acid, isononanoic acid, capric acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, and naphthenic acid.
Examples of the unsaturated aliphatic monocarboxylic acid include 9-hexadecenoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, cis-9, 12-octadecadienoic acid, 9,12, 15-octadecatrienoic acid, 6,9, 12-octadecatrienoic acid, 9,11, 13-octadecatrienoic acid, eicosanoic acid, 8, 11-eicosadienoic acid, 5,8, 11-eicosatrienoic acid, 5,8,11, 14-eicosatetraenoic acid, eleostearic acid, linoleic acid, soybean oleic acid, resin acid, tall oil fatty acid, abietic acid, neoabietic acid, palustric acid, pimaric acid, and dehydroabietic acid.
Examples of the aliphatic dicarboxylic acid having 2 to 25 carbon atoms include saturated aliphatic dicarboxylic acids and unsaturated aliphatic dicarboxylic acids.
Examples of saturated aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid.
Examples of the unsaturated aliphatic dicarboxylic acid include fumaric acid and maleic acid.
The aliphatic carboxylic acid having 2 to 25 carbon atoms is preferably an aliphatic monocarboxylic acid or an aliphatic dicarboxylic acid, more preferably an aliphatic monocarboxylic acid, and even more preferably a saturated aliphatic monocarboxylic acid. The use of the saturated aliphatic monocarboxylic acid has little effect on sulfur crosslinking of the rubber, and can prevent deterioration of rubber physical properties of the vulcanized rubber.
Among the saturated fatty acids, saturated aliphatic monocarboxylic acids having 2 to 20 carbon atoms are preferable, and 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid, and octadecanoic acid are more preferable.
The metal carboxylate (1) can be produced, for example, according to the following method.
The manufacturing method 1: (a) a method for producing a polycarbonate by directly reacting an aliphatic carboxylic acid having 2 to 25 carbon atoms with at least one selected from the group consisting of (b-1) an oxide of a metal (bismuth, copper, antimony, silver, niobium, zirconium), (b-2) a hydroxide of a metal (bismuth, copper, antimony, silver, niobium, zirconium), and (b-3) a carbonate of a metal (bismuth, copper, antimony, silver, niobium, zirconium) (direct method).
The manufacturing method 2: the process comprises reacting (a) an aliphatic carboxylic acid having 2 to 25 carbon atoms with sodium hydroxide in the presence of water to obtain a sodium salt of the aliphatic carboxylic acid, and then reacting the sodium salt of the aliphatic carboxylic acid with at least one selected from (c-1) a sulfate of a metal (bismuth, copper, antimony, silver, niobium, zirconium), (c-2) a chloride of a metal (bismuth, copper, antimony, silver, niobium, zirconium), and (c-3) a nitrate of a metal (bismuth, copper, antimony, silver, niobium, zirconium) (double decomposition method).
Examples of the oxide (b-1) of the metal (bismuth, copper, antimony, silver, niobium, zirconium) include bismuth (III) oxide, copper (I) oxide, copper (II) oxide, antimony (III) oxide, antimony (V) oxide, silver (I) oxide, silver (II) oxide, silver (III) oxide, niobium (IV) oxide, niobium (V) oxide, and zirconium oxide.
Examples of the hydroxide (b-2) of a metal (bismuth, copper, antimony, silver, niobium, zirconium) include copper (II) hydroxide and zirconium hydroxide.
Examples of the carbonate (b-3) of metals (bismuth, copper, antimony, silver, niobium, zirconium) include bismuth (III) carbonate, bismuth (III) carbonate oxide, and copper (II) carbonate.
Examples of the sulfate (c-1) of a metal (bismuth, copper, antimony, silver, niobium, zirconium) include copper (II) sulfate and zirconium sulfate.
Examples of the chloride (c-2) of a metal (bismuth, copper, antimony, silver, niobium, zirconium) include bismuth (III) oxychloride, copper (I) chloride, copper (II) chloride, antimony (III) chloride, antimony (V) chloride, silver (I) chloride, and niobium (V) chloride.
Examples of the nitrate (c-3) of metals (bismuth, copper, antimony, silver, niobium, zirconium) include bismuth (III) nitrate, bismuth (III) subnitrate, and silver (I) nitrate.
In the production method 1, the reaction temperature for reacting the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms with the compounds (b-1) to (b-3) is usually 50 to 150 ℃. The reaction time is usually 1 to 20 hours.
In the production method 2, the reaction temperature for reacting the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms with sodium hydroxide in the presence of an organic solvent is usually 20 to 100 ℃. The reaction time is usually 1 to 5 hours.
In the production method 2, the reaction temperature for reacting the sodium salt of the aliphatic carboxylic acid with the compounds (c-1) to (c-3) is usually 20 to 100 ℃. The reaction time is usually 1 to 5 hours.
In production method 2, after the sodium salt of an aliphatic carboxylic acid is reacted with the compounds (c-1) to (c-3), the aqueous layer in the reaction system is separated. Subsequently, the solvent present in the oil layer was removed by distillation under reduced pressure to obtain metal carboxylate (1).
Next, the compound (2) represented by the formula (a) is described in detail.
The (RCOO) in the compound (2) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms. When the number of carbon atoms of the residue of the aliphatic carboxylic acid is less than 2, compatibility between the rubber component and the compound (2) is poor, and as a result, adhesion between the vulcanized rubber and the metal is lowered. When the number of carbon atoms of the residue of the aliphatic carboxylic acid is more than 25, the compound (2) is difficult to synthesize. In addition, if so, the compound (2) is difficult to disperse in the rubber component or the vulcanized rubber is difficult to adsorb to the surface of the steel cord, and as a result, the adhesion between the vulcanized rubber and the metal is lowered.
Examples of the residue of the aliphatic monocarboxylic acid having 2 to 25 carbon atoms include residues of aliphatic monocarboxylic acids, and preferred examples thereof are residues derived from aliphatic monocarboxylic acids described for the metal carboxylate (1).
Among the residues of aliphatic carboxylic acids, the residues of saturated aliphatic monocarboxylic acids are preferred. The residue-promoting compound (2) using a saturated aliphatic monocarboxylic acid is easily dispersed around the steel cord or the vulcanized rubber is easily adsorbed to the surface of the steel cord. Among the residues of saturated aliphatic monocarboxylic acids, the residues of saturated aliphatic monocarboxylic acids having 2 to 20 carbon atoms are preferable, and the residues of 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid, and octadecanoic acid are more preferable.
M in the compound represented by the formula (a) is a metal species, and specifically bismuth, copper, antimony, silver, niobium or zirconium. Among the metal species, bismuth, copper, antimony, and silver are preferable, and bismuth and copper are more preferable, from the viewpoint that an adhesion promoter for better adhesion between the steel cord and the rubber can be obtained even under wet heat conditions.
X in the compound (2) represented by the formula (A) is an integer of (valence of M-1).
Z in the compound (2) represented by the formula (A) has a structure selected from the group consisting of the above-mentioned formulae (Z-1) to (Z-4).
Among the above, the structure represented by the formula (z-1) is preferable from the viewpoint of easily obtaining an adhesion promoter which exhibits high adhesion between a vulcanized rubber and a metal.
The compound (2) represented by the formula (a) can be produced, for example, by mixing and heating an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms with an inorganic acid ester (d), an acid (e) and a metal compound m (f), and then removing the resulting volatile ester (g).
The aliphatic carboxylic acid (a) having 2 to 25 carbon atoms includes the above aliphatic monocarboxylic acid having 2 to 25 carbon atoms.
The inorganic acid ester (d) includes (d-1) a boric acid ester of a lower alcohol having 1 to 5 carbon atoms, (d-2) a metaboric acid ester of a lower alcohol having 1 to 5 carbon atoms, (d-3) a phosphoric acid ester of a lower alcohol having 1 to 5 carbon atoms, and (d-4) a phosphorous acid ester of a lower alcohol having 1 to 5 carbon atoms.
Examples of the boric acid ester (d-1) of a lower alcohol include trimethyl borate, triethyl borate, tripropyl borate, and tributyl borate.
Examples of the metaborate ester (d-2) of a lower alcohol include trimethyl metaborate, triethyl metaborate, tripropyl metaborate, and tributyl metaborate.
Examples of the phosphoric acid ester (d-3) of a lower alcohol include methyl phosphate, ethyl phosphate, propyl phosphate, and butyl phosphate.
Examples of the phosphite ester (d-4) of a lower alcohol include methyl phosphite, ethyl phosphite, propyl phosphite, and butyl phosphite.
Among the above, metaborate (d-2) of lower alcohols is preferable from the viewpoint of preventing corrosion of uncured aged metals.
The acid (e) is an acid capable of forming a volatile ester (g) with a lower alcohol residue having 1 to 5 carbon atoms present in the inorganic acid ester (d). Specifically, examples thereof include acetic acid, propionic acid and butyric acid.
The metal compound m (f) is a metal source of the compound (2), and examples thereof which may be used herein include the oxide (b-1), the hydroxide (b-2) and the carbonate (b-3) described above for the production method of the metal carboxylate (1).
The metal compound M (f) as a metal source is used in a proportion of, for example, 20 to 100 parts by mass relative to 100 parts by mass of the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms.
The inorganic acid ester (d) is used in an amount of, for example, 10 to 50 parts by mass per 100 parts by mass of the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms.
The amount of the acid (e) is, for example, 10 to 50 parts by mass per 100 parts by mass of the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms.
The mixing of the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms, the inorganic acid ester (d), the acid (e), and the metal compound m (f) may be performed in one step or may be performed in a plurality of steps.
One example of a method of mixing components in multiple steps is a manufacturing method including the following first step and second step.
The first step is a step of mixing and heating an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms, an acid (e), and a metal compound M (f) to obtain a reaction product (h).
The second step is a step of removing water from the reaction system containing the reaction product (h) produced in the first step, then adding the inorganic acid ester (d) to the reaction system from which water has been removed, and reacting the reaction product (h) and the inorganic acid ester (d).
By producing the compound (2) through the above two steps, the inorganic acid ester (d) can be prevented from being hydrolyzed by the water formed in the first step, and the compound (2) can be efficiently produced.
In the production method comprising the above two steps, the temperature at which the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms, the inorganic acid ester (d), the acid (e) and the metal compound m (f) are reacted is, for example, 100 to 250 ℃, preferably 150 to 220 ℃. The reaction time is, for example, 1 to 20 hours, preferably 1 to 5 hours.
The content of the rubber-metal adhesion promoter in the rubber composition is preferably 1.0 to 5.0 parts by mass, more preferably 1.5 to 4.5 parts by mass, even more preferably 1.7 to 4.0 parts by mass, relative to 100 parts by mass of the rubber component, from the viewpoint of improving the adhesion between the vulcanized rubber and the metal and improving the durability of the metal-rubber composite and the tire.
The metal content in the rubber composition is preferably 15 to 55 mass%, more preferably 23 to 50 mass%, even more preferably 25 to 45 mass%, from the viewpoint of improving the adhesion between the vulcanized rubber and the metal and improving the durability of the metal-rubber composite and the tire.
[4,4' -Diphenylmethane bismaleimide ]
The rubber composition of the present invention comprises 4,4' -diphenylmethane bismaleimide.
When the rubber composition does not contain 4,4' -diphenylmethane bismaleimide, a vulcanized rubber excellent in adhesion to metal cannot be obtained, and the rubber-metal composite and the tire are not excellent in durability. In addition, when the rubber composition does not contain 4,4' -diphenylmethane bismaleimide, uncured aged metal corrosion proceeds, and rubber-metal adhesion deteriorates.
The content of 4,4' -diphenylmethane bismaleimide in the rubber composition is preferably 0.3 to 2.0 parts by mass, more preferably 0.3 to 1.5 parts by mass, and even more preferably 0.5 to 1.0 part by mass, relative to 100 parts by mass of the rubber component.
The rubber composition of the present invention preferably contains at least one selected from the group consisting of disodium hexamethylene dithiosulfate dihydrate, 1, 3-bis (citraconimidomethyl) benzene, and 3-hydroxy-N' - (1, 3-dimethylbutylidene) -2-naphthoic acid hydrazide (referred to as component B).
When the rubber composition contains one or two or all of disodium hexamethylenedithiosulfate dihydrate, 1, 3-bis (citraconimidomethyl) benzene, and 3-hydroxy-N' - (1, 3-dimethylbutylidene) -2-naphthoic acid hydrazide, the rubber-metal adhesion is more improved, and the durability of the rubber-metal composite and the tire is more improved.
Preferably, component B comprises at least disodium hexamethylene dithiosulfate dihydrate.
The content of the component B in the rubber composition is preferably 0.3 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass, even more preferably 1.0 to 2.0 parts by mass, relative to 100 parts by mass of the rubber component.
[ cobalt-containing Material ]
The rubber composition of the present invention may or may not contain a cobalt-containing material.
Examples of the cobalt salt of an organic acid include cobalt naphthenate, cobalt stearate, cobalt neodecanoate, cobalt resinate (cobalt resinate), cobalt versatate, cobalt tallate (tail-oil-acid cobalt), cobalt oleate, cobalt linoleate, cobalt linolenate, and cobalt palmitate. Examples of cobalt metal complexes include cobalt acetylacetonate.
As described above, although a cobalt-containing material has been used so far to obtain the effect of rubber-metal adhesion, the rubber composition of the present invention contains a rubber-metal adhesion promoter containing bismuth or the like, and therefore, the rubber-metal adhesion is excellent although the cobalt-containing material is not contained. In addition, the rubber composition does not contain a cobalt-containing material, so that corrosion of uncured aged metal can be prevented, and environmental load can be reduced.
Specifically, the cobalt atom content in the rubber composition of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.01% by mass or less, and still more preferably 0% by mass.
Further, the cobalt element content in the rubber component is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.01% by mass or less, and further more preferably 0% by mass.
[ Filler ]
The rubber composition of the present invention preferably contains a filler.
When the rubber composition of the present invention contains a filler, the reinforcement of the vulcanized rubber obtained from the rubber composition of the present invention can be improved, and the durability of the rubber-metal composite and the tire can be improved.
The kind of the filler is not particularly limited, and for example, a reinforcing filler for reinforcing the rubber composition is used. Examples of reinforcing fillers include metal oxides such as silica, alumina, titania and zirconia, as well as aluminum hydroxide and carbon black.
One kind or two or more kinds of the filler may be used alone.
The filler preferably contains at least one selected from the group consisting of carbon black and silica from the viewpoint of improving the reinforcement of the vulcanized rubber and improving the durability of the rubber-metal composite and the tire.
(carbon Black)
The carbon black is not particularly limited and may be appropriately selected depending on the intended use. For example, the carbon black is preferably of FEF, SRF, HAF, ISAF or SAF grade, more preferably of HAF, ISAF or SAF grade, even more preferably of HAF grade.
The carbon black content in the rubber composition is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, relative to 100 parts by mass of the rubber component.
When the filler content in the rubber composition is 30 parts by mass or more with respect to 100 parts by mass of the rubber component, the reinforcement of the vulcanized rubber is excellent, and when the filler content is 90 parts by mass or less, hysteresis due to friction of the filler material can be more reduced.
(silica)
Examples of the silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), colloidal silica, calcium silicate, and aluminum silicate. Of these, wet silica is preferably used. A single kind of silica may be used alone or in combination of two or more kinds. The silica content is preferably 1.0 to 10 parts by mass, more preferably 2.0 to 9.0 parts by mass, and even more preferably 4.0 to 8.0 parts by mass, relative to 100 parts by mass of the rubber component.
[ Sulfur ]
The rubber composition of the present invention preferably contains sulfur.
The sulfur is not particularly limited, and examples thereof include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur.
From the viewpoint of further improving the rubber-metal adhesiveness and further improving the durability of the rubber-metal composite and the tire, the sulfur content in the rubber composition is preferably 2 to 10 parts by mass, more preferably 3 to 9 parts by mass, and even more preferably 4 to 8 parts by mass with respect to 100 parts by mass of the rubber component.
[ vulcanization accelerators ]
The rubber composition of the present invention may contain a vulcanization accelerator which further accelerates vulcanization of the rubber component.
Specifically, examples thereof include thiuram-based, guanidine-based, aldehyde/amine-based, aldehyde/ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, dithiocarbamate-based, and xanthate-based vulcanization accelerators. One kind of the vulcanization accelerator alone or two or more kinds of the vulcanization accelerators may be used.
From the viewpoint of further improving the rubber-metal adhesion and further improving the durability of the rubber-metal composite and the tire, the content of the vulcanization accelerator in the rubber composition is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the rubber component.
Along with the rubber component, the rubber-metal adhesion promoter, 4' -diphenylmethane bismaleimide, the filler and sulfur therein, the rubber composition of the present invention may optionally contain, as required, any other compounding agent commonly used in the rubber industry field, for example, softening agent, stearic acid, anti-aging agent, zinc oxide, silane coupling agent, resin, wax and oil, in addition to disodium hexamethylenedithiosulfate dihydrate and 1, 3-bis (citraconimidomethyl) benzene, appropriately selected within the range not departing from the object of the present invention.
[ preparation of rubber composition ]
The rubber composition of the present invention can be produced by blending the above components and mixing them using a mixer such as a banbury mixer, a roll or an internal mixer.
Here, the blending amount of each component is the same as the amount described above as the content in the rubber composition.
The mixing of the components may be carried out all in one stage or separately in two or more stages. For example, in the case of kneading in two stages, the maximum temperature in the first kneading stage is preferably 130 to 160 ℃ and the maximum temperature in the second stage is preferably 90 to 120 ℃.
The rubber composition of the present invention is preferably used as a rubber composition for coating a metal cord such as a typical steel cord.
< rubber-Metal composite >
The rubber-metal composite of the present invention comprises a vulcanized rubber of the rubber composition of the present invention and a metal.
By coating a metal with the rubber composition of the present invention and vulcanizing the rubber composition, a rubber-metal composite in which the metal is coated with a vulcanized rubber can be obtained. The rubber composition of the present invention may cover at least a part of the metal, but from the viewpoint of improving the durability of the rubber-metal composite, the rubber composition preferably covers the entire surface of the metal.
The metal of the rubber-metal composite is not particularly limited, and includes various metal members such as a metal cord and a metal plate.
The rubber-metal composite can be advantageously used as a reinforcing material for rubber products such as various vehicle tires, conveyor belts, and hoses, which are particularly required to have strength. In particular, the composite body can be advantageously used as a belt, carcass and wire chafer reinforcing member for various radial tires for vehicles.
For coating the steel cord, for example, the following method is employable.
Preferably, a predetermined number of brass-plated steel cords are arranged in parallel at a predetermined pitch, the steel cords are coated with an uncrosslinked rubber sheet of the rubber composition of the present invention having a thickness of about 0.5mm from the upper and lower sides of the steel cords, and vulcanized at a temperature of, for example, about 160 ℃ for about 20 minutes. In this way, the resulting composite of the rubber composition and the steel cord has excellent rubber-metal adhesion.
The above-mentioned steel cord may be any one of steel monofilament and multifilament (twisted cord or aligned strand cord), and the shape thereof is not particularly limited. The twisted structure of the twisted steel cord is also not particularly limited, and examples thereof include a single-twist structure, a double-twist structure, a layer-twist structure, and a composite-twist structure of the double-twist structure and the layer-twist structure.
From the viewpoint of favorably ensuring the adhesiveness with the rubber composition, the steel cord is preferably subjected to surface treatment, for example, by surface plating or by treatment with an adhesive.
The surface of the steel wire may be plated. The kind of plating is not particularly limited, and examples thereof include zinc (Zn) plating, copper (Cu) plating, tin (Sn) plating, brass (copper-zinc (Cu-Zn)) plating, and bronze (copper-tin (Cu-Sn)) plating, and ternary plating such as copper-zinc-tin (Cu-Zn-Sn) plating and copper-zinc-cobalt (Cu-Zn-Co) plating. Of these, brass plating and copper-zinc-cobalt ternary plating are preferable.
Further, it is also possible to use a steel wire in which, for example, surface N atoms account for 2 atomic% or more and 60 atomic% or less and the surface Cu/Zn ratio is 1 or more and 4 or less. The metal wire 1 includes a case where the amount of phosphorus contained as an oxide is 7.0 atomic% or less inward in the wire radius direction until the wire outermost layer 5nm as a proportion of the total amount other than the amount of C.
In the case of using the adhesive treatment, for example, the adhesive treatment with a trade name "Chemlock" (registered trademark) of Lord Corporation is preferable.
The rubber composition of the present invention can prevent corrosion of metal even after a predetermined time has elapsed after the metal is coated, and therefore, for example, an article can be circulated in a state where a metal cord is coated with the rubber composition, and vulcanization can be performed at a circulating destination to manufacture a rubber-metal composite. The rubber-metal composite produced in this way prevents metal corrosion, and hardly loses rubber-metal adhesion, and is therefore excellent in durability.
< tire >
The tire of the present invention comprises the rubber-metal composite of the present invention.
Since the tire of the present invention comprises the rubber-metal composite of the present invention, the tire of the present invention is excellent in durability.
The method for producing the tire of the present invention is not particularly limited as long as the method can produce a tire comprising the rubber-metal composite of the present invention.
Generally, a rubber composition containing various components is processed into various members at an unvulcanized stage, and then the members are bonded and shaped on a tire shaping machine according to a conventional method to form a green tire. The green tire is heated and pressurized in a vulcanizer to manufacture a tire. For example, the rubber composition of the present invention is kneaded, the resulting rubber composition is spread on a steel cord to laminate an unvulcanized belt layer, an unvulcanized carcass and other unvulcanized members, and the resulting unvulcanized laminate is vulcanized to obtain a tire.
As the gas for filling the tire, usual air, air adjusted in oxygen partial pressure, and inert gases such as nitrogen, argon, and helium can be used.
< conveyor belt, hose, and crawler >
The conveyor belt of the present invention comprises the rubber-metal composite of the present invention.
The hose of the present invention comprises the rubber-metal composite of the present invention.
The track of the present invention comprises the rubber-metal composite of the present invention.
The conveyor belt, hose and crawler of the present invention are excellent in durability because they comprise a rubber-metal composite excellent in durability and rubber-metal adhesion. The manufacturing method of the conveyor belt, hose and crawler of the present invention is not particularly limited.
Examples
[ preparation of rubber composition ]
The constituent components were kneaded according to the blending formulations shown in tables 2 to 10 to prepare rubber compositions. In tables 2 to 10, the blank part means a value of 0. The details of the components shown in tables 2 to 10 are as follows.
Natural rubber: RSS #3
CB 1: carbon black, manufactured by Tokai Carbon Co., Ltd., product name "Seast SO"
CB 2: carbon black, manufactured by Tokai Carbon co., ltd, under the trade name "Seast 300"
CB 3: carbon black, manufactured by Tokai Carbon co., ltd, under the trade name "Seast 600"
Silicon dioxide: manufactured by Tosoh Silica Corporation under the trade name "Nipsil VN 3"
Coupling agent: manufactured by Evonik Degussa Japan, trade name "Si-69"
Vulcanization accelerator DCBS: manufactured by Ouchi Shinko Chemical Industry co., ltd., trade name: Nocceler-DZ "
Vulcanization accelerator CBS: manufactured by Ouchi Shinko Chemical Industry co., ltd., trade name: "Nocceler-CZ"
Vulcanization accelerator TBSI: manufactured by Ouchi Shinko Chemical Industry co., ltd., trade name: Nocceler-NS "
BMI: 4,4' -bismaleimide diphenylmethane manufactured by Otsuka Chemical Co., Ltd
Disodium hexamethylene dithiosulfate dihydrate: manufactured by Eastman Corporation under the trade name "Duralnk-HTS"
1, 3-bis (citraconimidomethyl) benzene: manufactured by Lanxess Japan, trade name "Perkalink-900"
3-hydroxy-N' - (1, 3-dimethylbutylidene) -2-naphthoic acid hydrazide: manufactured by Otsuka Chemical Co., Ltd., BMH
Resorcinol resin: manufactured by Taoka Chemical Co., Ltd., product name "Sumikanol 620"
Methylene donor compound (HMMMM): manufactured by Cytec Industries, Inc., trade name "CYREZ 964"
Neodecanoic acid Co: cobalt neodecanoate, structure of the following (i), molecular weight 401.5
Neodecanoic acid Bi: bismuth neodecanoate, structure of (iii) below, molecular weight 722.8, wherein the metal species is the metal carboxylate of bismuth (1)
< production of rubber-Metal composite >
Steel cords (1X 5X 0.25mm (wire diameter)) plated with brass (Cu:63 mass%, Zn:37 mass%) were arranged in parallel at intervals of 12.5mm and covered with the prepared rubber composition to obtain an unvulcanized rubber-metal composite precursor (unvulcanized steel cord top roll) having a thickness of 5 mm. Thereafter, rapidly, the rubber-metal composite precursor was vulcanized at 145 ℃ for 40 minutes to produce a rubber-metal composite (ordinary composite) containing a vulcanized rubber.
In the rubber-metal adhesion evaluation of uncured aged adhesion as mentioned in [4] below, a rubber-metal composite sample for evaluation was prepared as follows.
After preparing a rubber-metal composite precursor (unvulcanized steel cord top roll) having a thickness of 5mm, the rubber-metal composite precursor (unvulcanized steel cord top roll) was left in an environment having a temperature of 40 ℃ and a humidity of 80% for 1 week, and then the rubber-metal composite precursor was vulcanized at 145 ℃ for 140 minutes to produce a rubber-metal composite containing a vulcanized rubber (an uncured composite for aging evaluation).
[ evaluation ]
The samples were evaluated according to the method shown in table 1.
Specifically, the test is as follows.
1. Rubber-to-metal adhesion
The rubber-metal adhesion was evaluated in four adhesion states of [1] initial adhesion, [2] wet heat adhesion, [3] thermal adhesion and [4] uncured post-aging adhesion.
In [1] initial adhesion evaluation and [4] uncured adhesion evaluation after aging, a steel cord was drawn from the produced rubber-metal composite (ordinary composite and uncured composite for evaluation after aging) in an atmosphere of-65 ± 5 ℃.
In [2] wet heat adhesion evaluation, the produced rubber-metal composite (ordinary composite) was degraded at 75 ℃ and 95% RH, and then a steel cord was drawn from the rubber-metal composite in an atmosphere of-65. + -. 5 ℃.
In [3] evaluation of thermal adhesiveness, the produced rubber-metal composite (ordinary composite) was degraded in an environment of 100 ℃ for 60 days under a nitrogen partial pressure of 0.1MPa (in the case where the atmospheric pressure is 0.1 MPa), and then a steel cord was drawn from the rubber-metal composite in an atmosphere of-65. + -. 5 ℃.
2. Durability
The durability of the rubber-metal composite was evaluated from the viewpoint of the elastic modulus and tensile properties of the vulcanized rubber.
(rubber deterioration resistance index)
After the uncured aging for rubber-metal adhesion evaluation, a vulcanized rubber was cut out from the rubber-metal composite used in [4] adhesion evaluation, and the elongation at break (EB) (unit:%) and tensile strength (TB) (unit: MPa) of the resultant vulcanized rubber were measured. Assuming that the value EB × TB of comparative example 1 is an index 100, a value calculated by multiplying the obtained EB by TB is converted into the index EB × TB of the examples and comparative examples. The larger the index EB × TB is, the more excellent the durability of the rubber-metal composite is.
Elongation at break (EB) (unit:%) and tensile strength (TB) (unit: MPa) were determined as follows.
Elongation at Break (EB) (Unit:%) tensile Strength (TB) (Unit: MPa)
Each rubber composition was formed into a sheet (2. + -. 0.3mm thick, 15 cm. times.15 cm) and then vulcanized at 145 ℃ for 40 minutes. The resulting vulcanizate was aged at 70 ℃ for 3 days at an oxygen partial pressure of 0.5MPa (in the case of an atmospheric pressure of 0.1 MPa). Subsequently, the sample was punched to obtain JIS #3 sheet. The tensile strength of each sample was measured at 100 ℃ under the condition of 500 mm/min using a Strograph AP3 manufactured by Toyo Seiki Kogyo co., ltd., and elongation at break × strength at break were calculated. Based on the results of comparative example 5 as 100, the results of examples and comparative examples are expressed as indexes.
(modulus of elasticity of rubber, tan. delta.)
A rectangular vulcanized rubber sheet was cut out from the rubber-metal composite (ordinary composite) used in the initial adhesion evaluation of the rubber-metal adhesion evaluation of [1 ]. The dynamic elastic modulus (E') and tan δ of the obtained rectangular vulcanized rubber sheet were measured using a viscoelasticity measuring device (spectrometer manufactured by Toyo Seiki Kogyo co., ltd.). With respect to the measurement conditions, a sine wave was imparted to the sample at a temperature of 100 ℃ and a frequency of 15Hz, under a single-sided tensile strain of 5%.
The dynamic elastic moduli (E ') and tan δ of comparative example 5 were each represented as 100, and the dynamic elastic moduli (E') and tan δ of the examples and comparative examples were represented as indices. The larger index value means the more excellent durability of the rubber-metal composite.
The results are shown in tables 2 to 10.
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Watch 10
Industrial applicability
The rubber composition of the present invention is excellent in rubber-metal adhesion and can produce a rubber-metal composite excellent in durability, and therefore the rubber-metal composite produced using the rubber composition of the present invention is suitable not only for producing various tires such as heavy duty tires, for example, truck tires and bus tires and passenger car tires, but also for producing conveyor belts, hoses and crawler belts.
Claims (17)
1. A rubber composition, comprising:
a rubber component (a) comprising a rubber,
4,4' -diphenylmethane bismaleimide, and
a rubber-metal adhesion promoter comprising at least one selected from the group consisting of: (1) a metal carboxylate having 2 to 25 carbon atoms, and wherein the metal species is selected from the group consisting of bismuth, copper, antimony, silver, niobium, and zirconium; and (2) a compound represented by the following formula (a):
[(RCOO)xMO]3Z (A)
wherein Z is a structure selected from the group consisting of formulae (Z-1) to (Z-4), M is bismuth, copper, antimony, silver, niobium or zirconium, (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, and x is an integer of (valence-1 of M).
2. The rubber composition according to claim 1, further comprising at least one selected from the group consisting of disodium hexamethylene dithiosulfate dihydrate, 1, 3-bis (citraconimidomethyl) benzene, 3-hydroxy-N' - (1, 3-dimethylbutylidene) -2-naphthoic acid hydrazide.
3. The rubber composition according to claim 1 or 2, comprising a filler containing at least one selected from the group consisting of carbon black and silica.
4. The rubber composition according to any one of claims 1 to 3, wherein the rubber component comprises a natural rubber.
5. The rubber composition according to any one of claims 1 to 4, wherein the rubber-metal adhesion promoter comprises the metal carboxylate (1), and the metal species of the metal carboxylate (1) is bismuth or copper.
6. The rubber composition according to any one of claims 1 to 5, wherein the rubber-metal adhesion promoter comprises the metal carboxylate (1), and the aliphatic carboxylic acid in the metal carboxylate (1) is an aliphatic monocarboxylic acid or an aliphatic dicarboxylic acid.
7. The rubber composition according to claim 6, wherein the aliphatic monocarboxylic acid is a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms.
8. The rubber composition according to claim 7, wherein the saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms is 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid.
9. The rubber composition according to any one of claims 1 to 8, wherein the rubber-metal adhesion promoter comprises the compound (2), and M in the compound (2) is bismuth or copper.
10. The rubber composition according to any one of claims 1 to 9, wherein the rubber-metal adhesion promoter comprises the compound (2), and Z in the compound (2) is a structure represented by formula (Z-1).
11. The rubber composition according to any one of claims 1 to 10, wherein the rubber-metal adhesion promoter comprises the compound (2), and (RCOO) in the compound (2) is a residue of a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms.
12. The rubber composition according to claim 11, wherein (RCOO) in the compound (2) is a residue of 2-ethylhexanoic acid, a residue of neodecanoic acid, a residue of hexadecanoic acid or a residue of octadecanoic acid.
13. A rubber-metal composite comprising the vulcanized rubber of the rubber composition described in any one of claims 1 to 12 and a metal.
14. A tire comprising the rubber-metal composite of claim 13.
15. A conveyor belt comprising the rubber-metal composite of claim 13.
16. A hose comprising the rubber-metal composite of claim 13.
17. A track comprising the rubber-metal composite of claim 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019181067 | 2019-09-30 | ||
| JP2019-181067 | 2019-09-30 | ||
| PCT/JP2020/036976 WO2021065931A1 (en) | 2019-09-30 | 2020-09-29 | Rubber composition, rubber/metal composite, tire, conveyor belt, hose, and crawler |
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| CN114450335A true CN114450335A (en) | 2022-05-06 |
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| CN202080067811.7A Pending CN114450335A (en) | 2019-09-30 | 2020-09-29 | Rubber composition, rubber-metal composite, tire, conveyor belt, hose, and crawler belt |
Country Status (4)
| Country | Link |
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| EP (1) | EP4039500A4 (en) |
| JP (1) | JPWO2021065931A1 (en) |
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| JP6996592B2 (en) * | 2020-06-23 | 2022-01-17 | 横浜ゴム株式会社 | Pneumatic tires |
| JPWO2022215507A1 (en) * | 2021-04-05 | 2022-10-13 | ||
| CN114807936A (en) * | 2022-04-18 | 2022-07-29 | 南京工业职业技术大学 | Cobalt-containing composite coating for steel cord and preparation method thereof |
| WO2024014114A1 (en) * | 2022-07-12 | 2024-01-18 | Dic株式会社 | Rubber composition, coating material, and adhesive |
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| JP2008024826A (en) * | 2006-07-21 | 2008-02-07 | Bridgestone Corp | Pneumatic tire using rubber composition |
| WO2010126143A1 (en) * | 2009-04-30 | 2010-11-04 | 株式会社ブリヂストン | Tire |
| US20140020808A1 (en) * | 2011-04-26 | 2014-01-23 | Sumitomo Chemical Company, Limited | Rubber composition |
| JP2016041779A (en) * | 2014-08-15 | 2016-03-31 | 株式会社ブリヂストン | Tire rubber composition and tire |
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| CN106687517A (en) * | 2014-09-12 | 2017-05-17 | Dic株式会社 | Rubber-metal adhesion promoter, rubber composition, and tire |
| JP2019112746A (en) * | 2017-12-25 | 2019-07-11 | 株式会社ブリヂストン | Metal cord-rubber composite, belt for tire, carcass for tire, and tire |
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| JP2002194139A (en) * | 2000-10-19 | 2002-07-10 | Bridgestone Corp | Rubber composition and tire containing polymaleimide |
| JP4328046B2 (en) * | 2000-11-09 | 2009-09-09 | 株式会社ブリヂストン | tire |
| JP6532768B2 (en) * | 2015-06-18 | 2019-06-19 | 株式会社ブリヂストン | Steel cord-rubber complex |
-
2020
- 2020-09-29 WO PCT/JP2020/036976 patent/WO2021065931A1/en unknown
- 2020-09-29 CN CN202080067811.7A patent/CN114450335A/en active Pending
- 2020-09-29 EP EP20871341.2A patent/EP4039500A4/en active Pending
- 2020-09-29 JP JP2021551324A patent/JPWO2021065931A1/ja active Pending
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| JP2008024826A (en) * | 2006-07-21 | 2008-02-07 | Bridgestone Corp | Pneumatic tire using rubber composition |
| WO2010126143A1 (en) * | 2009-04-30 | 2010-11-04 | 株式会社ブリヂストン | Tire |
| US20140020808A1 (en) * | 2011-04-26 | 2014-01-23 | Sumitomo Chemical Company, Limited | Rubber composition |
| JP2016041779A (en) * | 2014-08-15 | 2016-03-31 | 株式会社ブリヂストン | Tire rubber composition and tire |
| CN106687518A (en) * | 2014-09-12 | 2017-05-17 | Dic株式会社 | Rubber-metal adhesion promoter, rubber composition, and tire |
| CN106687517A (en) * | 2014-09-12 | 2017-05-17 | Dic株式会社 | Rubber-metal adhesion promoter, rubber composition, and tire |
| JP2019112746A (en) * | 2017-12-25 | 2019-07-11 | 株式会社ブリヂストン | Metal cord-rubber composite, belt for tire, carcass for tire, and tire |
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| EP4039500A4 (en) | 2022-11-23 |
| WO2021065931A1 (en) | 2021-04-08 |
| JPWO2021065931A1 (en) | 2021-04-08 |
| EP4039500A1 (en) | 2022-08-10 |
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